JPS6234027B2 - - Google Patents
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- Publication number
- JPS6234027B2 JPS6234027B2 JP55075690A JP7569080A JPS6234027B2 JP S6234027 B2 JPS6234027 B2 JP S6234027B2 JP 55075690 A JP55075690 A JP 55075690A JP 7569080 A JP7569080 A JP 7569080A JP S6234027 B2 JPS6234027 B2 JP S6234027B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- hydrogen
- attributed
- peak
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- -1 alkyl lithium derivatives Chemical class 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 150000003335 secondary amines Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 39
- 239000001257 hydrogen Substances 0.000 abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract 2
- XYQWMCXCCWXTBD-UHFFFAOYSA-N 3-formyl-4-methylpent-3-enoic acid Chemical compound CC(C)=C(C=O)CC(O)=O XYQWMCXCCWXTBD-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000003756 stirring Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- RHDGNLCLDBVESU-UHFFFAOYSA-N but-3-en-4-olide Chemical compound O=C1CC=CO1 RHDGNLCLDBVESU-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- JQWPNLIKQCENRW-UHFFFAOYSA-M 2-(2-methoxy-5-oxooxolan-3-yl)propan-2-yl-triphenylphosphanium;iodide Chemical compound [I-].COC1OC(=O)CC1C(C)(C)[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 JQWPNLIKQCENRW-UHFFFAOYSA-M 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- DUJYZGXBCPOPDD-UHFFFAOYSA-N 1-methyl-4-propan-2-ylsulfonylbenzene Chemical compound CC(C)S(=O)(=O)C1=CC=C(C)C=C1 DUJYZGXBCPOPDD-UHFFFAOYSA-N 0.000 description 1
- FGLBSLMDCBOPQK-UHFFFAOYSA-N 2-nitropropane Chemical compound CC(C)[N+]([O-])=O FGLBSLMDCBOPQK-UHFFFAOYSA-N 0.000 description 1
- KGICTMCXRILIDV-UHFFFAOYSA-N 4-(2-chloropropan-2-yl)-5-[(3-phenoxyphenyl)methoxy]oxolan-2-one Chemical compound CC(C)(Cl)C1CC(=O)OC1OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGICTMCXRILIDV-UHFFFAOYSA-N 0.000 description 1
- QHAPONCMFJQXEN-UHFFFAOYSA-N 4-hydroxy-6,6-dimethyl-3-oxabicyclo[3.1.0]hexan-2-one Chemical compound O=C1OC(O)C2C1C2(C)C QHAPONCMFJQXEN-UHFFFAOYSA-N 0.000 description 1
- DUAZKLYNTLDKQK-UHFFFAOYSA-N 5-hydroxy-2(5h)-furanone Chemical compound OC1OC(=O)C=C1 DUAZKLYNTLDKQK-UHFFFAOYSA-N 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 108700032832 MP-33 Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003844 furanonyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- YIYBQIKDCADOSF-UHFFFAOYSA-N pentenoic acid group Chemical class C(C=CCC)(=O)O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- HHBXWXJLQYJJBW-UHFFFAOYSA-M triphenyl(propan-2-yl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 HHBXWXJLQYJJBW-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/74—Unsaturated compounds containing —CHO groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Furan Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、置換ペンテン酸、その製造法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to substituted pentenoic acids and processes for their production.
まず、本発明の主題は、次式
の３−ホルミル−４−メチルペンタ−３−エン−
１−酸にある。 First, the subject of the present invention is the following formula 3-formyl-4-methylpent-3-ene-
1- In acid.
また、本発明の主題は、次式
（ここでＺは求電子性基を表わす）
の誘導体を次式
（ここでＲは、アルコールROHの残基Ｒを表わ
す）
の誘導体と反応させ、次いで生じた次式
の化合物に塩基性試剤を作用させることを特徴と
する式の３−ホルミル−４−メチルペンタ−３
−エン−１−酸の製造法にある。 Furthermore, the subject matter of the present invention is that the following formula (Here, Z represents an electrophilic group) The derivative of (where R represents the residue R of the alcohol ROH) and then the resulting formula 3-formyl-4-methylpenta-3 of the formula characterized by reacting a basic reagent with a compound of
-Production method of en-1-acid.
さらに詳しくは、本発明の主題は、基ＺがNO2
基であり、そして化合物とを第二アミン、第
三アミン、水酸化第四アンモニウム及び炭酸アル
カリよりなる群から選ばれる塩基の存在下に反応
させることを特徴とする前記の製造法にある。 More particularly, the subject of the invention provides that the group Z is NO 2
and the compound is reacted in the presence of a base selected from the group consisting of secondary amines, tertiary amines, quaternary ammonium hydroxides and alkali carbonates.
化合物とを反応させる際に存在させる第三
アミンとしては、トリエチルアミンが有利に用い
られる。 Triethylamine is advantageously used as the tertiary amine present when reacting with the compound.
また、本発明の主題は、基Ｚがヒドロキシル基
であり、そして化合物とを放射線照射下で又
はラジカル開始剤の存在下で反応させることを特
徴とする製造法にある。 The subject of the invention is also a process for the preparation, characterized in that the group Z is a hydroxyl group and the reaction with the compound is carried out under radiation irradiation or in the presence of a radical initiator.
ラジカル開始剤としては、過酸化ベンゾイル、
アゾビスイソブチロニトリル、過酸化ジ−ｔ−ブ
チル、過安息香酸ｔ−ブチル又は過酸化ジラウロ
イルが有利に用いられる。 As a radical initiator, benzoyl peroxide,
Azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate or dilauroyl peroxide are preferably used.
また、本発明の主題は、基Ｚがアリールスルホ
ニル基であり、そして化合物とを有機溶媒中
で強塩基の存在下で反応させることを特徴とする
製造法にある。 The subject of the invention is also a process for the preparation, characterized in that the group Z is an arylsulfonyl group and the reaction with the compound is carried out in an organic solvent in the presence of a strong base.
アリールスルホニル基のアリール基は、特にｐ
−トリル基である。 The aryl group of the arylsulfonyl group is particularly p
-Tolyl group.
また、本発明の主題は、基Ｚがハロトリアリー
ルスホニオ基であり、そして化合物とを有機
溶媒中で強塩基の存在下で反応させることを特徴
とする上記の製造法にある。 The subject of the invention is also the abovementioned production process, characterized in that the group Z is a halotriarylsulfonio group and that the reaction with the compound is carried out in an organic solvent in the presence of a strong base.
ハロトリアリールホスホニオ基は、特に、ヨー
ドトリフエニルホスホニオ基である。 A halotriarylphosphonio group is in particular an iodotriphenylphosphonio group.
また、本発明の主題は、基Ｚがアリールスルホ
ニル基又はハロトリアリールホスホニオ基であ
り、そして強塩基がアルキルリチウム誘導体、ア
ルカリアミド、水素化アルカリ及びアルカリアル
コラートよりなる群から選ばれ、使用する溶媒が
テトラヒドロフラン、ジメチルスルホキシド、ジ
メトキシエタン、ジメチルホルムアミド、ヘキサ
メチルホスホルアミド、芳香族炭化水素及びシク
ロアルカンよりなる群から選ばれることを特徴と
する上記の製造法にある。 A subject of the invention is also the use in which the group Z is an arylsulfonyl group or a halotriarylphosphonio group and the strong base is selected from the group consisting of alkyllithium derivatives, alkali amides, alkali hydrides and alkali alcoholates. The above method is characterized in that the solvent is selected from the group consisting of tetrahydrofuran, dimethylsulfoxide, dimethoxyethane, dimethylformamide, hexamethylphosphoramide, aromatic hydrocarbons and cycloalkanes.
Ｚがアリールスルホニル基又はハロトリアリー
ルホスホニオ基であるときは、化合物ととの
間の反応は、テトラヒドロフランとシクロヘキサ
ンとの混合物中でブチルリチウムの存在下で行な
われる。 When Z is an arylsulfonyl group or a halotriarylphosphonio group, the reaction between the compound and is carried out in the presence of butyllithium in a mixture of tetrahydrofuran and cyclohexane.
本発明の方法に従えば、化合物と反応させる
塩基性試剤は、特に、含水メタノール媒体中で用
いられる炭酸ナトリウムである。 According to the method of the invention, the basic agent reacted with the compound is, in particular, sodium carbonate used in an aqueous methanol medium.
本発明の式の３−ホルミル−４−メチルペン
タ−３−エン−１−酸は、殺虫性エステルの合成
中間体である次式
（ここでＷは水素原子又はアキラルであつてよい
アルコールR1OHの残基R1を表わす）
の化合物の製造に使用することができる。このよ
うな製造法は、無水条件下に３−ホルミル−４−
メチルペンタ−３−エン−１−酸を有機溶媒中で
ハロゲン化リチウムLiXの存在下に水素酸HX
（ここでＸはハロゲン原子を表わす）と反応させ
て次式
の化合物を得、これをアキラルなアルコール
R1OHと反応させて次式
のラセミ形化合物（これは誘導体と同様にテト
ラヒドロフランの４と５の置換基の間でtrans立
体配置を有する）を得るか、或るいはキラルなア
ルコールR1OHと反応させて式の化合物を二つ
の所期のジアステレオマーの混合物の形で得、こ
の混合物は物理的方法によつてその成分に分離す
ることができ、次いでR1がアキラルであるとき
はラセミ形態にあり又はR1がキラルであるとき
は光学活性形態にある式の化合物（式の化合
物は、後者の場合には、ジアステレオマーの一方
又は他方の状態にある）を塩基性試剤と反応させ
て次式
の二環式化合物をR1がそれぞれアキラルか又は
キラルな残基であるかどうかによつてラセミ形態
か或るいはそのエナンチオマー形の一方又は他方
の形態で得（この化合物の４位置の絶対配置並び
にこれから生じる１及び５位置での立体配置は使
用するジアステレオマーの立体化学により決定
される）、次いで所望により式のエーテルを酸
性媒体中で、絶対配置を完全に保持して、加水分
解して次式ＶA
の６・６−ジメチル−４−ヒドロキシ−３−オキ
サビシクロ〔３・１・０〕ヘキサン−２−オンを
得ることを特徴とするものである。 3-formyl-4-methylpent-3-en-1-acid of the formula of the present invention is an intermediate for the synthesis of insecticidal esters of the following formula: (where W represents a hydrogen atom or the residue R 1 of an alcohol R 1 OH which may be achiral). Such a production method involves producing 3-formyl-4- under anhydrous conditions.
Methylpent-3-en-1-acid was converted into hydric acid HX in the presence of lithium halide LiX in an organic solvent.
(Here, X represents a halogen atom) to react with the following formula and convert it into an achiral alcohol.
React with R 1 OH to form the following formula (which, like the derivatives, has a trans configuration between the 4 and 5 substituents of tetrahydrofuran) or reacts with a chiral alcohol R 1 OH to give a compound of formula obtained in the form of a mixture of the two desired diastereomers, which mixture can be separated into its components by physical methods and then in racemic form when R 1 is achiral or in racemic form when R 1 is chiral. A compound of formula in optically active form when The bicyclic compound of can be obtained in racemic form or in one or the other of its enantiomeric forms depending on whether R 1 is an achiral or chiral residue, respectively (the absolute configuration of the 4-position and the resulting configuration at the 1 and 5 positions is determined by the stereochemistry of the diastereomer used), then optionally the ether of the formula is hydrolyzed in an acidic medium with perfect retention of the absolute configuration. The following formula V A 6,6-dimethyl-4-hydroxy-3-oxabicyclo[3.1.0]hexan-2-one is obtained.
このような製造の例を実施例の部に示す。 Examples of such production are shown in the Examples section.
ところで、６・６−ジメチル−４−ヒドロキシ
−３−オキサビシクロ〔３・１・０〕ヘキサン−
２−オンを非常に複雑な化合物の菊酸から製造す
るのを可能にする半合成法は既に存在していた
（例えばフランス国特許第1580474号を参照）。 By the way, 6,6-dimethyl-4-hydroxy-3-oxabicyclo[3.1.0]hexane-
Semi-synthetic methods already existed that made it possible to prepare 2-ones from the very complex compound chrysanthemum acid (see, for example, French Patent No. 1,580,474).
本発明者は、ここに、式の化合物によつて、
ラセミ形又は光学活性形の６・６−ジメチル−４
−ヒドロキシ−３−オキサビシクロ〔３・１・
０〕ヘキサン−２−オン又はそのエーテルの全合
成法を完成した。この方法は容易に入手できる薬
剤を使用し、そしてその工程数は少ないものであ
る。 The inventors herein understand that by a compound of formula:
6,6-dimethyl-4 in racemic or optically active form
-Hydroxy-3-oxabicyclo [3.1.
0] A complete synthesis method for hexan-2-one or its ether was completed. This method uses readily available agents and has a small number of steps.
高活性を持つ多くの殺虫性エステルの合成中間
体（例えば、フランス国特許第2185612号を参
照）となる６・６−ジメチル−４−ヒドロキシ−
３−オキサビシクロ〔３・１・０〕ヘキサン−２
−オンのような化合物の全合成法は、特に有益で
ある。 6,6-dimethyl-4-hydroxy- which is an intermediate in the synthesis of many insecticidal esters with high activity (see e.g. French Patent No. 2185612).
3-Oxabicyclo[3.1.0]hexane-2
Total synthetic methods for compounds such as -ones are particularly useful.
下記の例は本発明を例示するが、これを何ら制
限しない。 The examples below illustrate the invention but do not limit it in any way.
例 １
３−ホルミル−４−メチルペンタ−３−エン−
１−酸
工程Ａ：dl−trans−４−（２−ニトロ−２−プロ
ピル）−５−メトキシテトラヒドロフラン−２
−オン
９c.c.の２−ニトロプロパン、７ｇの５−メトキ
シ−２・５−ジヒドロフラン−２−オン−３−エ
ン及び１c.c.のトリエチルアミンを20〜25℃で70時
間かきまぜ、反応混合物をりん酸モノナトリウム
水溶液で洗い、ベンゼンで抽出し、乾燥し、減圧
下に濃縮乾固し、その残留物をイソプロピルエー
テルで溶解し、結晶化を開始し、かきまぜながら
０℃に冷却し、分離し、8.24ｇの結晶質生成物を
得る。MP33℃。Example 1 3-formyl-4-methylpent-3-ene-
1-Acid step A: dl-trans-4-(2-nitro-2-propyl)-5-methoxytetrahydrofuran-2
-one 9 c.c. of 2-nitropropane, 7 g of 5-methoxy-2,5-dihydrofuran-2-one-3-ene and 1 c.c. of triethylamine were stirred at 20-25°C for 70 hours and reacted. The mixture was washed with aqueous monosodium phosphate solution, extracted with benzene, dried, concentrated to dryness under reduced pressure, the residue was dissolved in isopropyl ether to initiate crystallization, cooled to 0 °C with stirring, Separation yields 8.24 g of crystalline product. MP33℃.
分析：C8H13NO5＝203.18
計算：Ｃ％47.29 Ｈ％6.45 Ｎ％6.87
実測： 47.10 6.50
6.70
MNRスペクトル
gem−メチルの水素に帰する1.6ppmののピー
ク、シクロペンチルの３及び４位の水素に帰する
2.0−3.17ppmのピーク、
シクロペンチルの５位の水素に帰する5.25−
5.28ppmのピーク、
メトキシの水素に帰する3.5ppmのピーク。Analysis: C 8 H 13 NO 5 = 203.18 Calculation: C% 47.29 H% 6.45 N% 6.87 Actual measurement: 47.10 6.50
6.70 MNR spectrum gem-1.6ppm peak attributed to hydrogen of methyl, attributed to hydrogen at 3 and 4 positions of cyclopentyl
2.0−3.17 ppm peak, 5.25− attributed to hydrogen at position 5 of cyclopentyl
5.28ppm peak, 3.5ppm peak attributed to methoxy hydrogen.
工程Ｂ：３−ホルミル−４−メチルペンタ−３−
エン−１−酸
18.9ｇの炭酸ナトリウムを180c.c.の水に溶解
し、０℃に冷却し、18.2ｇの上で得たニトロラク
トンを一度に加え、25c.c.のメタノールに溶解す
る。周囲温度で120時間放置した後、反応混合物
をエチルエーテルで洗い、０℃に冷却し、不活性
雰囲気下に注意しながら若干の濃硫酸をPH１ま
で加え、クロロホルム、次いで酢酸エチルで抽出
し、一緒にした有機相を乾燥し、減圧下に濃縮乾
固して9.5ｇの粗生成物を得、これを水から結晶
化して7.4ｇの純生成物を得る。MP＝102℃。Step B: 3-formyl-4-methylpenta-3-
Ene-1-acid Dissolve 18.9 g of sodium carbonate in 180 c.c. of water, cool to 0°C, add 18.2 g of the nitrolactone obtained above in one portion and dissolve in 25 c.c. of methanol. . After standing for 120 hours at ambient temperature, the reaction mixture was washed with ethyl ether, cooled to 0 °C, carefully added with some concentrated sulfuric acid to pH 1 under an inert atmosphere, extracted with chloroform and then with ethyl acetate, and combined. The organic phase is dried and concentrated to dryness under reduced pressure to obtain 9.5 g of crude product, which is crystallized from water to obtain 7.4 g of pure product. MP=102℃.
分析：C7H10C3＝142.156
計算：Ｃ％59.14 Ｈ％7.09
実測： 59.20 7.0
NMRスペクトル
５位の水素に帰する2.0ppmのピーク、
４位のメチルの水素に帰する2.26ppmのピー
ク、
２位の水素に帰する3.38ppmのピーク、
ホルミルの水素に帰する10.13ppmのピーク。Analysis: C 7 H 10 C 3 = 142.156 Calculation: C% 59.14 H% 7.09 Actual measurement: 59.20 7.0 NMR spectrum 2.0 ppm peak attributed to hydrogen at position 5, 2.26 ppm peak attributed to methyl hydrogen at position 4, A peak of 3.38ppm attributed to hydrogen at the 2nd position, and a peak of 10.13ppm attributed to formyl hydrogen.
例
３−ホルミル−４−メチルペンタ−３−エン−
１−酸
工程Ａ：dl−trans−４−（２−ヒドロキシ−２−
プロピル）−５−（３−フエノキシフエニル）メ
トキシテトラヒドロフラン−２−オン
3.5ｇの５−（３−フエノキシフエニル）メトキ
シ−２・５−ジヒドロフラン−２−オンを100c.c.
のイソプロパノール中で不活性雰囲気下にかきま
ぜながら加熱還流し、300mgの過酸化ベンゾイル
を25mgづつ１時間半にわたり規則的に加え、40〜
50℃で減圧下に濃縮乾固し、その残留物をシリカ
でクロマトグラフイーし、次いでベンゼン／酢酸
エチル混合物（８：２）で溶離し、3.7ｇの粗生
成物を回収し、これをイソプロピルエーテルで溶
解し、白色結晶を得る。MP＝50〜55℃。Example 3-formyl-4-methylpent-3-ene-
1-Acid step A: dl-trans-4-(2-hydroxy-2-
3.5 g of 5-(3-phenoxyphenyl)methoxy-2,5-dihydrofuran-2-one was added to 100 c.c.
of isopropanol with stirring under an inert atmosphere, 300 mg of benzoyl peroxide was added regularly in 25 mg portions over 1.5 hours,
Concentrated to dryness under reduced pressure at 50°C, the residue was chromatographed on silica and then eluted with a benzene/ethyl acetate mixture (8:2) to recover 3.7 g of crude product, which was purified by isopropyl Dissolve with ether to obtain white crystals. MP=50-55℃.
分析：C20H22O3＝342.39
計算：Ｃ％70.06 Ｈ％6.4
実測： 69.9 6.5
NMRスペクトル
メチルの水素に帰する1.18及び1.21ppmのピー
ク、
シクロペンチルの３及び４位の水素に帰する
2.16−2.75ppmのピーク、
ベンジルメチレンの水素に帰する4.48−4.35及
び4.8−5ppmのピーク
シクロペンチルの５位の水素に帰する5.59−
5.58ppmのピーク、
芳香族核の水素に帰する6.85−7.5ppmのピー
ク、
ヒドロキシルの水素に帰する1.5ppmのピー
ク。Analysis: C 20 H 22 O 3 = 342.39 Calculation: C% 70.06 H% 6.4 Actual measurement: 69.9 6.5 NMR spectrum 1.18 and 1.21 ppm peaks attributed to hydrogen of methyl, attributed to hydrogen at 3 and 4 positions of cyclopentyl
Peak at 2.16-2.75ppm, peak at 4.48-4.35 and 4.8-5ppm attributed to hydrogen of benzylmethylene 5.59- attributed to hydrogen at position 5 of cyclopentyl
A peak at 5.58 ppm, a peak at 6.85-7.5 ppm attributed to the hydrogen of the aromatic nucleus, and a peak at 1.5 ppm attributed to the hydrogen of the hydroxyl.
この例の開始時で用いた５−（３−フエノキシ
フエニル）メトキシ−２・５−ジヒドロフラン−
２−オンは次のように製造した。 5-(3-Phenoxyphenyl)methoxy-2,5-dihydrofuran- used at the beginning of this example
2-one was produced as follows.
12ｇの５−ヒドロキシ−２（5H）−フラノン、
250c.c.のベンゼン、25ｇのｍ−フエノキシベンジ
ルアルコール及び200mgのｐ−トルエンスルホン
酸を混合し、反応混合物中のベンゼンを蒸留し、
同一量の乾燥ベンゼンで数回置換しながらかきま
ぜ、２時間後に周囲温度で冷却せしめ、重炭酸ナ
トリウム飽和溶液で洗い、次いで水洗し、乾燥
し、減圧下に濃縮乾固し、39.7ｇの油状物を得、
これをシリカでクロマトグラフイーし、ベンゼ
ン／酢酸エチル混合物（９：１）で溶離して精製
し、24.9ｇの所期化合物を回収する。 12 g of 5-hydroxy-2(5H)-furanone,
Mix 250 c.c. of benzene, 25 g of m-phenoxybenzyl alcohol and 200 mg of p-toluenesulfonic acid, distill the benzene in the reaction mixture,
Stirring with several displacements of the same amount of dry benzene was allowed to cool at ambient temperature after 2 hours, washed with saturated sodium bicarbonate solution, then water, dried and concentrated to dryness under reduced pressure, yielding 39.7 g of an oil. obtained,
This is purified by chromatography on silica, eluting with a benzene/ethyl acetate mixture (9:1), and 24.9 g of the expected compound are recovered.
NMRスペクトル
フラノンの４位の水素に帰する7.3−7.4ppmの
ピーク、
フラノンの３位の水素に帰する6.18−6.32ppm
のピーク、
フラノンの５位の水素に帰する6.03ppmのピー
ク、
メトキシの水素に帰する4.58−4.76及び4.85−
5.12ppmのピーク、
芳香族核に帰する6.92−7.5ppmのピーク。NMR spectrum 7.3-7.4ppm peak attributed to hydrogen at position 4 of furanone, 6.18-6.32ppm attributed to hydrogen at position 3 of furanone
peak at 6.03 ppm attributed to hydrogen at position 5 of furanone, 4.58−4.76 and 4.85− attributed to hydrogen of methoxy
A peak at 5.12ppm, a peak at 6.92-7.5ppm attributed to aromatic nuclei.
工程Ｂ：３−ホルミル−４−メチルペンタ−３−
エン−１−酸
619mgの炭酸ナトリウムを６c.c.の水に溶解し、
０℃に冷却し、１ｇの上で得られたヒドロキシラ
クトンと２c.c.のメタノールをかきまぜながら加
え、周囲温度で19時間接触させた後、エチルエー
テルで洗い、０℃に冷却し、若干の濃硫酸をゆつ
くりと加え、メタノール及びクロロホルムで抽出
し、有機相を一緒にし、乾燥し、減圧下に濃縮乾
固し、245mgの粗生成物を得、これを再結晶して
102℃で融解する生成物を得る。Step B: 3-formyl-4-methylpenta-3-
Ene-1-acid Dissolve 619 mg of sodium carbonate in 6 c.c. of water,
Cooled to 0°C, added 1 g of the hydroxylactone and 2 c.c. of methanol with stirring, left in contact for 19 hours at ambient temperature, washed with ethyl ether, cooled to 0°C and added some Concentrated sulfuric acid was slowly added, extracted with methanol and chloroform, the organic phases were combined, dried, and concentrated to dryness under reduced pressure to obtain 245 mg of crude product, which was recrystallized.
A product is obtained which melts at 102°C.
例
３−ホルミル−４−メチルペンタ−３−エン−
１−酸
工程Ａ：dl−trans−４−（２−ｐ−トルエンスル
ホニル−２−プロピル）−５−メトキシテトラ
ヒドロフラン−２−オン
500mgのイソプロピルｐ−トリルスルホンと10
c.c.の無水テトラヒドロフランを不活性雰囲気下に
かきまぜながら混合し、−70℃に冷却し、1.3c.c.の
1.95Mのブチルリチウムのヘキサン溶液をゆつく
りと加え、−70℃で半時間かきまぜ、次いで287mg
の５−メトキシ−２・５−ジヒドロフラン−２−
オンを４c.c.のテトラヒドロフランに溶解してなる
ものを10分間で加え、−70℃に１時間保ち、反応
混合物を０℃のりん酸モノナトリウム水溶液上に
注ぎ、塩化メチレンで抽出し、水洗し、乾燥し、
減圧下に濃縮乾固し、その残留物をイソプロピル
エーテルで結晶化し、490mgの白色結晶を得る。
MP＝129℃。Example 3-formyl-4-methylpent-3-ene-
1-Acid Step A: dl-trans-4-(2-p-toluenesulfonyl-2-propyl)-5-methoxytetrahydrofuran-2-one 500 mg of isopropyl p-tolylsulfone and 10
cc of anhydrous tetrahydrofuran was mixed with stirring under an inert atmosphere, cooled to -70°C, and 1.3 cc of anhydrous tetrahydrofuran was mixed with stirring under an inert atmosphere.
Slowly add 1.95M hexane solution of butyllithium, stir at -70℃ for half an hour, then add 287mg
5-methoxy-2,5-dihydrofuran-2-
A solution of 4 c.c. and dry,
Concentrate to dryness under reduced pressure, and crystallize the residue from isopropyl ether to obtain 490 mg of white crystals.
MP=129℃.
分 析
計算：Ｃ％57.67 Ｈ％6.45 Ｓ％10.26
実測： 57.6 6.5
10.1
NMRスペクトル
gem−メチルの水素に帰する1.27−1.32ppmの
ピーク、
芳香族上のメチルの水素に帰する2.46ppmのピ
ーク、
シクロペンチルの３及び４位の水素に帰する
2.75ppmのピーク、
シクロペンチルの５位の水素に帰する5.58ppm
のピーク、
メトキシの水素に帰する3.51ppmのピーク、
芳香族の３及び５位の水素に帰する7.28−
7.42ppmのピーク、
芳香族の２及び６位の水素に帰する7.66−
7.8ppmのピーク。Analysis Calculation: C%57.67 H%6.45 S%10.26 Actual measurement: 57.6 6.5
10.1 NMR spectrum 1.27-1.32 ppm peak attributed to gem-methyl hydrogen, 2.46 ppm peak attributed to methyl hydrogen on aromatic, 3- and 4-position hydrogen of cyclopentyl
Peak at 2.75ppm, 5.58ppm attributed to hydrogen at position 5 of cyclopentyl
peak at 3.51 ppm attributed to methoxy hydrogen, 7.28- peak attributed to hydrogen at the 3 and 5 positions of aromatic
Peak at 7.42 ppm, 7.66− attributed to aromatic 2 and 6 hydrogens
7.8ppm peak.
工程Ｂ：３−ホルミル−４−メチルペンタ−３−
エン−１−酸
250mgの上で得た生成物、４c.c.の水、0.8c.c.のメ
タノール及び250mgの炭酸ナトリウムを周囲温度
で２日間かきまぜる。エーテルで洗浄した後、水
性相を1N塩酸によりPH３〜3.5まで酸性化し、塩
化ナトリウムで飽和させ、クロロホルムで抽出
し、乾燥し、減圧下に濃縮乾固し、87mgの所期生
成物を得る。MP＝102℃。Step B: 3-formyl-4-methylpenta-3-
Ene-1-acid 250 mg of the product obtained above, 4 c.c. of water, 0.8 cc of methanol and 250 mg of sodium carbonate are stirred at ambient temperature for 2 days. After washing with ether, the aqueous phase is acidified with 1N hydrochloric acid to PH 3-3.5, saturated with sodium chloride, extracted with chloroform, dried and concentrated to dryness under reduced pressure, giving 87 mg of the expected product. MP=102℃.
この生成物は、別の方法で得た３−ホルミル−
４−メチルペンタ−３−エン−１−酸と全ての点
で同等である。 This product is 3-formyl-
Equivalent in all respects to 4-methylpent-3-en-1-acid.
例
３−ホルミル−４−メチルペンタ−３−エン−
１−酸
工程Ａ：よう化〔１−（５−メトキシ−２−オキ
ソ−４・５−ジヒドロ−3H−フラン−４−イ
ル）−１−メチル−１−エチル〕トリフエニル
ホスホニウム
(a) イリドの製造
３ｇのよう化トリフエニルイソプロピルホス
ホニウムを40c.c.のテトラヒドロフランに加えて
なる懸濁液に、3.5c.c.の2Mブチルリチウムのシ
クロヘキサン溶液を一度で加え、周囲温度で10
分間かきまぜ、イリド溶液（溶液Ａ）を得る。Example 3-formyl-4-methylpent-3-ene-
1-Acid step A: Iodide [1-(5-methoxy-2-oxo-4,5-dihydro-3H-furan-4-yl)-1-methyl-1-ethyl]triphenylphosphonium (a) ylide To a suspension of 3 g triphenylisopropylphosphonium iodide in 40 c.c.
Stir for a minute to obtain a ylide solution (solution A).
(b) イリドのフラノンに対する付加
0.800ｇの５−メトキシ−２・５−ジヒドロ
フラン−２−オン−３−エンを50c.c.のテトラヒ
ドロフランに溶解して−60℃に冷却した溶液
に、−60℃に冷却した溶液Ａを不活性雰囲気下
にゆつくりと加える。10分間かきまぜ、反応混
合物をりん酸モノナトリウム水溶液と氷との混
合物上に注ぎ、エーテルで洗い、塩化メチレン
で抽出し、乾燥し、減圧下に濃縮乾固し、約
140℃で融解する3.4ｇのホスホニウム塩を得
る。(b) Addition of ylide to furanone 0.800 g of 5-methoxy-2,5-dihydrofuran-2-one-3-ene was dissolved in 50 c.c. of tetrahydrofuran and cooled to -60°C. Solution A, cooled to 60°C, is slowly added under an inert atmosphere. Stir for 10 minutes, pour the reaction mixture onto a mixture of aqueous monosodium phosphate and ice, wash with ether, extract with methylene chloride, dry, and concentrate to dryness under reduced pressure to give approx.
3.4 g of phosphonium salt is obtained which melts at 140°C.
分析：C26H8IO3P＝546.37
計算： Ｃ％57.15 Ｈ％5.16 Ｉ％23.24 Ｐ％5.67
実測：
57.3 5.2 22.4
5.3
NMRスペクトル
りんのβ位メチルの水素に帰する1.63−1.80−
1.95−2.10ppmのピーク、
フラノンの３及び４位炭素上の水素に帰する
2.22−3.33ppmのピーク、
メトキシの水素に帰する3.23ppmのピーク、
フラノンの５位水素に帰する5.46−5.54ppmの
ピーク、
芳香族核の水素に帰する7.81−7.92ppmのピー
ク。Analysis: C 26 H 8 IO 3 P=546.37 Calculation: C%57.15 H%5.16 I%23.24 P%5.67 Actual measurement:
57.3 5.2 22.4
5.3 NMR spectrum 1.63−1.80− attributed to hydrogen at β-methyl of phosphorus
Peak at 1.95-2.10ppm, attributed to hydrogen on carbons 3 and 4 of furanone
A peak at 2.22-3.33ppm, a peak at 3.23ppm attributed to the hydrogen of methoxy, a peak at 5.46-5.54ppm attributed to the hydrogen at the 5-position of furanone, a peak at 7.81-7.92ppm attributed to the hydrogen of the aromatic nucleus.
工程Ｂ：３−ホルミル−４−メチルペンタ−３−
エン−１−酸
0.700ｇのよう化〔１−（５−メトキシ−２−オ
キソ−４・５−ジヒドロ−3H−フラン−４−イ
ル）−１−メチル−１−エチル〕トリフエニルホ
スホニウムを１c.c.のメタノールに溶解してなる溶
液に、0.700ｇの炭酸ナトリウムを８c.c.の水に溶
解してなる溶液を加え、20℃で２時間かきまぜ、
生じた不溶物を別して除去し、液をPH２まで
酸性化し、塩化ナトリウムで飽和し、クロロホル
ムで抽出し、濃縮乾固し、イソプロピルエーテル
で精製し、0.095ｇの３−ホルミル−４−メチル
ペンタ−３−エン−１−酸を得る。MP＝102℃。Step B: 3-formyl-4-methylpenta-3-
1 c of [1-(5-methoxy-2-oxo-4,5-dihydro-3H-furan-4-yl)-1-methyl-1-ethyl]triphenylphosphonium iodide of 0.700 g of ene-1-acid. Add a solution of 0.700 g of sodium carbonate dissolved in 8 c.c. of water to a solution of .c. of methanol, stir at 20°C for 2 hours,
The resulting insoluble matter was removed separately, the solution was acidified to pH 2, saturated with sodium chloride, extracted with chloroform, concentrated to dryness and purified with isopropyl ether to give 0.095 g of 3-formyl-4-methylpenta-3. -en-1-acid is obtained. MP=102℃.
例
dl−６・６−ジメチル−４−ヒドロキシ−３−
オキサビシクロ〔３・１・０〕ヘキサン−２−
オン
工程Ａ：dl−trans−４−（２−クロル−２−プロ
ピル）−５−ヒドロキシテトラヒドロフラン−
２−オン
１ｇの例１、２、３又は４で得た３−ホルミル
−４−メチルペンタ−３−エン−１−酸、25c.c.の
無水エチルエーテル及び１ｇの乾燥塩化リチウム
を乾燥塩化水素気流中で−30℃で２時間、次いで
０℃で２時間かきまぜ、塩化水素の流れを止め、
周囲温度で48時間かきまぜ続け、54時間接触させ
た後、反応混合物を氷水中に注ぎ、デカンテーシ
ヨンし、ベンゼンで抽出し、乾燥し、減圧下に濃
縮乾固し、1.1ｇの粗生成物を得、これをシリカ
でクロマトグラフイーし、ベンゼン／酢酸エチル
混合物（１：１）で溶離し、545mgの結晶質生成
物を回収する。MP＝80℃。Example dl-6,6-dimethyl-4-hydroxy-3-
Oxabicyclo[3.1.0]hexane-2-
On step A: dl-trans-4-(2-chloro-2-propyl)-5-hydroxytetrahydrofuran-
2-one 1 g of 3-formyl-4-methylpent-3-en-1-acid obtained in Examples 1, 2, 3 or 4, 25 c.c. of anhydrous ethyl ether and 1 g of dry lithium chloride are dissolved in dry hydrogen chloride. Stir at −30 °C for 2 h in a stream of air, then at 0 °C for 2 h, stop the flow of hydrogen chloride,
After continued stirring at ambient temperature for 48 hours and contact for 54 hours, the reaction mixture was poured into ice water, decanted, extracted with benzene, dried, and concentrated to dryness under reduced pressure, yielding 1.1 g of crude product. This is chromatographed on silica, eluting with a benzene/ethyl acetate mixture (1:1), and 545 mg of crystalline product are recovered. MP=80℃.
分析：C7H11ClO3＝178.617
計算：Ｃ％47.07 Ｈ％6.21 Cl％19.85
実測： 47.2 6.2
19.5
NMRスペクトル
メチルの水素に帰する1.55及び1.6ppmのピー
ク、
環の３及び４位の水素に帰する2.42−2.92ppm
のピーク、
環の５位の水素に帰する5.82−5.89ppmのピー
ク、
ヒドロキシルの水素に帰する3.83ppmのピー
ク。Analysis: C 7 H 11 ClO 3 = 178.617 Calculation: C% 47.07 H% 6.21 Cl% 19.85 Actual measurement: 47.2 6.2
19.5 NMR spectrum Peaks at 1.55 and 1.6 ppm attributed to methyl hydrogen, 2.42-2.92 ppm attributed to hydrogen at the 3 and 4 positions of the ring
, a peak at 5.82-5.89ppm attributed to the hydrogen at the 5-position of the ring, and a peak at 3.83ppm attributed to the hydrogen in the hydroxyl.
工程Ｂ：４−（２−クロル−２−プロピル）−５−
〔（３−フエノキシフエニル）メトキシ〕テトラ
ヒドロフラン−２−オン
393mgの上で得た生成物、668mgのｍ−フエノキ
シベンジルアルコール、20mgのｐ−トルエンスル
ホン酸及び５c.c.のベンゼンを周囲温度で19時間か
きまぜ、少量の重炭酸ナトリウムで中和し、乾燥
し、減圧下に濃縮乾固し、1.18ｇの粗生成物を
得、これをシリカでクロマトグラフイーし、ベン
ゼンで溶離し、467mgの生成物を回収する。石油
エーテルで再結晶した後、ほぼ50℃の融点を有す
る。Step B: 4-(2-chloro-2-propyl)-5-
[(3-Phenoxyphenyl)methoxy]tetrahydrofuran-2-one 393 mg of the product obtained above, 668 mg of m-phenoxybenzyl alcohol, 20 mg of p-toluenesulfonic acid and 5 c.c. of benzene Stirred at ambient temperature for 19 hours, neutralized with a small amount of sodium bicarbonate, dried, and concentrated to dryness under reduced pressure to give 1.18 g of crude product, which was chromatographed on silica, eluting with benzene. , 467 mg of product is recovered. After recrystallization with petroleum ether, it has a melting point of approximately 50°C.
分析：C20H21ClO4＝360.84
計算：Ｃ％66.57 Ｈ％5.87 Cl％9.83
実測： 66.60 5.80
9.90
NMRスペクトル
メチルの水素に帰する1.5及び1.55ppmのピー
ク、
シクロペンチルの３及び４位の水素に帰する
2.55−2.72ppmのピーク、
シクロペンチルの５位の水素に帰する5.52−
5.56ppmのピーク、
芳香族核の水素に帰する6.92−7.5ppmのピー
ク、
ベンジルメチレンの水素に帰する4.47−4.66及
び4.77−4.97ppmのピーク。Analysis: C 20 H 21 ClO 4 =360.84 Calculation: C%66.57 H%5.87 Cl%9.83 Actual measurement: 66.60 5.80
9.90 NMR spectrum Peaks at 1.5 and 1.55 ppm attributed to hydrogen of methyl, attributed to hydrogen at positions 3 and 4 of cyclopentyl
Peak at 2.55−2.72 ppm, 5.52− attributed to hydrogen at position 5 of cyclopentyl
A peak at 5.56 ppm, a peak at 6.92-7.5 ppm attributed to the hydrogen of the aromatic nucleus, and a peak at 4.47-4.66 and 4.77-4.97 ppm attributed to the hydrogen of benzylmethylene.
工程Ｃ：dl−６・６−ジメチル−４−ヒドロキシ
−３−オキサビシクロ〔３・１・０〕ヘキサン
−２−オン
0.55c.c.の1Mジイソプロピルアミンのテトラヒ
ドロフラン溶液と５c.c.のテトラヒドロフランを約
−20℃に冷却し、0.25c.c.の2Mn−ブチルリチウム
のシクロヘキサン溶液を加え、温度を０℃に戻
し、次いで−60〜−70℃に冷却し、180mgの工程
Ｂで得た生成物を一度に加え、０℃に２時間加熱
した後、この温度で１時間保ち、反応混合物を冷
2N塩酸中に注ぎ、強くかきまぜながら20℃に17
時間放置し、デカンテーシヨンし、クロロホルム
で抽出し、乾燥し、濃縮乾固し、得られた残留物
をイソプロピルエーテル／石油エーテル混合物で
溶解し、水で抽出し、水性相を減圧下に濃縮乾固
して30mgの結晶質生成物を得る。MP＝80℃。Step C: dl-6.6-dimethyl-4-hydroxy-3-oxabicyclo[3.1.0]hexane-2-one 0.55 cc of 1M diisopropylamine in tetrahydrofuran and 5 cc. of tetrahydrofuran are combined to approx. Cool to 20 °C, add 0.25 cc of 2Mn-butyllithium in cyclohexane, bring the temperature back to 0 °C, then cool to -60 to -70 °C, and add 180 mg of the product obtained in step B at once. , heated to 0°C for 2 hours, then kept at this temperature for 1 hour, and the reaction mixture was cooled.
Pour into 2N hydrochloric acid and heat to 20℃ for 17 minutes while stirring vigorously.
Leave to stand for an hour, decantate, extract with chloroform, dry, concentrate to dryness, dissolve the residue obtained in an isopropyl ether/petroleum ether mixture, extract with water and concentrate the aqueous phase under reduced pressure. Dryness gives 30 mg of crystalline product. MP=80℃.
Claims (1)
１−酸。 ２ 次式 （ここでＺは求電子性基を表わす） の誘導体を次式 （ここでＲは、アルコールROHの残基Ｒを表わ
す） の誘導体と反応させ、次いで生じた次式 の化合物に塩基性試剤を作用させることを特徴と
する式 の３−ホルミル−４−メチルペンタ−３−エン−
１−酸の製造法。 ３ 基ＺがNO2基であり、そして化合物とを
第二アミン、第三アミン、水酸化第四アンモニウ
ム及び炭酸アルカリよりなる群から選ばれる塩基
の存在下に反応させることを特徴とする特許請求
の範囲第２項記載の方法。 ４ 基Ｚがヒドロキシル基であり、そして化合物
とを放射線照射下で又はラジカル開始剤の存
在下で反応させることを特徴とする特許請求の範
囲第２項記載の方法。 ５ 基Ｚがアリールスルホニル基であり、そして
化合物とを有機溶媒中で強塩基の存在下で反
応させることを特徴とする特許請求の範囲第２項
記載の方法。 ６ 基Ｚがハロトリアリールスルホニル基であ
り、そして化合物とを有機溶媒中で強塩基の
存在下で反応させることを特徴とする特許請求の
範囲第２項記載の方法。 ７ 強塩基がアルキルリチウム誘導体、アルカリ
アミド、水素化アルカリ及びアルカリアルコラー
トよりなる群から選ばれ、使用する溶媒がテトラ
ヒドロフラン、ジメチルスルホキシド、ジメトキ
シエタン、ジメチルホルムアミド、ヘキサメチル
ホスホルアミド、芳香族炭化水素及びシクロアル
カンよりなる群から選ばれることを特徴とする特
許請求の範囲第５又は６項記載の方法。 ８ 塩基性試剤が含水メタノール媒体中で用いら
れる炭酸ナトリウムであることを特徴とする特許
請求の範囲第２項記載の方法。[Claims] Linear formula 3-formyl-4-methylpent-3-ene-
1-acid. Quadratic equation (Here, Z represents an electrophilic group) The derivative of (where R represents the residue R of the alcohol ROH) and then the resulting formula A formula characterized by the action of a basic reagent on the compound of 3-formyl-4-methylpent-3-ene-
1-Production method of acid. 3. A patent claim characterized in that the group Z is an NO 2 group, and the compound is reacted with the compound in the presence of a base selected from the group consisting of secondary amines, tertiary amines, quaternary ammonium hydroxides, and alkali carbonates. The method according to item 2 of the scope. 4. Process according to claim 2, characterized in that the group Z is a hydroxyl group and the reaction with the compound is carried out under radiation irradiation or in the presence of a radical initiator. 5. The method according to claim 2, characterized in that the group Z is an arylsulfonyl group and the reaction with the compound is carried out in an organic solvent in the presence of a strong base. 6. The method according to claim 2, wherein the group Z is a halotriarylsulfonyl group and the reaction with the compound is carried out in an organic solvent in the presence of a strong base. 7. The strong base is selected from the group consisting of alkyl lithium derivatives, alkali amides, alkali hydrides and alkali alcoholates, and the solvent used is tetrahydrofuran, dimethyl sulfoxide, dimethoxyethane, dimethylformamide, hexamethylphosphoramide, aromatic hydrocarbons and The method according to claim 5 or 6, characterized in that the method is selected from the group consisting of cycloalkanes. 8. Process according to claim 2, characterized in that the basic reagent is sodium carbonate used in an aqueous methanol medium.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7914425A FR2458533A1 (en) | 1979-06-06 | 1979-06-06 | SUBSTITUTED PENTENOIC ACID, PROCESS FOR PREPARING THE SAME AND APPLICATION THEREOF TO THE PREPARATION OF SUBSTITUTED CYCLOPROPANE DERIVATIVES |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5629544A JPS5629544A (en) | 1981-03-24 |
| JPS6234027B2 true JPS6234027B2 (en) | 1987-07-24 |
Family
ID=9226263
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7569080A Granted JPS5629544A (en) | 1979-06-06 | 1980-06-06 | Novel subtituted pentenoic acid* its manufacture* use in manufacture of substituted cyclopropane derivative and novel compound obtained therefrom |
| JP62004212A Granted JPS63239279A (en) | 1979-06-06 | 1987-01-13 | Novel substituted tetrahydrofuran derivative |
| JP62004211A Granted JPS62161778A (en) | 1979-06-06 | 1987-01-13 | Manufacture of substituted cyclopropane derivative |
| JP2302825A Granted JPH03173880A (en) | 1979-06-06 | 1990-11-09 | Novel substituted tetrahydrofuran derivative |
Family Applications After (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62004212A Granted JPS63239279A (en) | 1979-06-06 | 1987-01-13 | Novel substituted tetrahydrofuran derivative |
| JP62004211A Granted JPS62161778A (en) | 1979-06-06 | 1987-01-13 | Manufacture of substituted cyclopropane derivative |
| JP2302825A Granted JPH03173880A (en) | 1979-06-06 | 1990-11-09 | Novel substituted tetrahydrofuran derivative |
Country Status (7)
| Country | Link |
|---|---|
| US (3) | US4556732A (en) |
| EP (3) | EP0023849B1 (en) |
| JP (4) | JPS5629544A (en) |
| AT (2) | ATE9225T1 (en) |
| CA (1) | CA1142958A (en) |
| FR (1) | FR2458533A1 (en) |
| HU (1) | HU180358B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01107723U (en) * | 1988-01-14 | 1989-07-20 |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2463134A1 (en) * | 1979-08-10 | 1981-02-20 | Roussel Uclaf | NOVEL SULFON COMPOUNDS COMPRISING A LACTON CYCLE, PROCESS FOR THE PREPARATION THEREOF AND THEIR USE FOR THE PREPARATION OF CYCLOPROPANE DERIVATIVES |
| FR2485000A1 (en) * | 1980-06-20 | 1981-12-24 | Roussel Uclaf | LOWER ALKYL 4-METHYL 3-FORMYL PENTENE 1-OATES, PROCESS FOR PREPARING THEM AND THEIR APPLICATION |
| US4673672A (en) * | 1985-10-28 | 1987-06-16 | Sandoz Pharmaceuticals Corp. | Substituted-[hydroxy(tetrahydro)-5-oxo-(2- and 3-furanyl or 2-thienyl)alkoxyphosphinyloxy]-alkanaminium hydroxide, inner salt oxides |
| FR2618781B2 (en) * | 1987-01-09 | 1990-05-04 | Roussel Uclaf | PROCESS FOR THE PREPARATION OF DERIVATIVES OF 4,4-DIMETHYL TETRAHYDRO PYR-2-ONE |
| US5032653A (en) * | 1988-06-28 | 1991-07-16 | Exxon Chemical Patents, Inc. | Direct synthesis by cationic polymerization of nitrogen-containing polymers |
| JPH02240033A (en) * | 1989-03-13 | 1990-09-25 | Daikin Ind Ltd | Novel monoterpene and derivative thereof |
| JPH0444346U (en) * | 1990-08-08 | 1992-04-15 | ||
| JPH069936U (en) * | 1992-02-24 | 1994-02-08 | 明和グラビア株式会社 | Decorative sticker sheet |
| JPH0585991U (en) * | 1992-04-14 | 1993-11-19 | 日本バイリーン株式会社 | Adhesive material for window glass |
| EP1221290B1 (en) | 2001-01-08 | 2005-04-13 | Calzaturificio S.C.A.R.P.A. S.p.A. | Ski boot |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE870252C (en) * | 1944-05-13 | 1953-03-12 | Guenther O Dr Schenck | Process for the preparation of ª † -oxocarboxylic acids |
| US2493676A (en) * | 1947-07-21 | 1950-01-03 | Staley Mfg Co A E | Pseudo esters of levulinic acid |
| US2485100A (en) * | 1948-09-25 | 1949-10-18 | Us Rubber Co | Lactonization of 2, 4-polyhalogenoalkanoic esters |
| US2726250A (en) * | 1951-05-15 | 1955-12-06 | Koege Kemisk Vaerk | 5-monosubstituted 2-oxo-2, 5-dihydrofurans |
| GB893322A (en) * | 1957-08-19 | 1962-04-04 | Unilever Ltd | Lactonols |
| NL301342A (en) * | 1962-12-08 | |||
| FR1362039A (en) * | 1963-04-17 | 1964-05-29 | Ct D Etudes Experimentales Et | New process for preparing succinic semi-aldehyde |
| FR1394863A (en) * | 1964-02-24 | 1965-04-09 | Electrochimie Soc | Process for the preparation of gamma formyl-carboxylic acids or their derivatives, and products obtained |
| US4132717A (en) * | 1977-08-09 | 1979-01-02 | Shell Oil Company | Enol lactone intermediate for the preparation of (1R,cis)-caronaldehydic acid |
| FR2463134A1 (en) * | 1979-08-10 | 1981-02-20 | Roussel Uclaf | NOVEL SULFON COMPOUNDS COMPRISING A LACTON CYCLE, PROCESS FOR THE PREPARATION THEREOF AND THEIR USE FOR THE PREPARATION OF CYCLOPROPANE DERIVATIVES |
| US4235780A (en) * | 1979-11-01 | 1980-11-25 | Fmc Corporation | Derivatives of 2H-pyran-2-one |
| US4342694A (en) * | 1979-11-01 | 1982-08-03 | Fmc Corporation | Processes for producing pyrethroid insecticide intermediates |
| FR2479213A1 (en) * | 1980-03-28 | 1981-10-02 | Roussel Uclaf | PROCESS FOR PREPARING PENTENOIC ACID HAVING ALDEHYDE FUNCTION |
-
1979
- 1979-06-06 FR FR7914425A patent/FR2458533A1/en active Granted
-
1980
- 1980-05-27 US US06/153,338 patent/US4556732A/en not_active Expired - Lifetime
- 1980-06-03 EP EP80400789A patent/EP0023849B1/en not_active Expired
- 1980-06-03 EP EP82200366A patent/EP0057491B1/en not_active Expired
- 1980-06-03 AT AT82200370T patent/ATE9225T1/en not_active IP Right Cessation
- 1980-06-03 EP EP82200370A patent/EP0057045B1/en not_active Expired
- 1980-06-03 AT AT82200366T patent/ATE8781T1/en active
- 1980-06-05 CA CA000353428A patent/CA1142958A/en not_active Expired
- 1980-06-05 HU HU80801423A patent/HU180358B/en not_active IP Right Cessation
- 1980-06-06 JP JP7569080A patent/JPS5629544A/en active Granted
-
1982
- 1982-07-01 US US06/394,457 patent/US4443617A/en not_active Expired - Lifetime
-
1984
- 1984-01-19 US US06/571,995 patent/US4500720A/en not_active Expired - Lifetime
-
1987
- 1987-01-13 JP JP62004212A patent/JPS63239279A/en active Granted
- 1987-01-13 JP JP62004211A patent/JPS62161778A/en active Granted
-
1990
- 1990-11-09 JP JP2302825A patent/JPH03173880A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01107723U (en) * | 1988-01-14 | 1989-07-20 |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE9225T1 (en) | 1984-09-15 |
| US4443617A (en) | 1984-04-17 |
| EP0057045B1 (en) | 1984-09-05 |
| FR2458533A1 (en) | 1981-01-02 |
| JPH02352B2 (en) | 1990-01-08 |
| EP0057045A3 (en) | 1982-08-18 |
| US4500720A (en) | 1985-02-19 |
| CA1142958A (en) | 1983-03-15 |
| JPH0321550B2 (en) | 1991-03-22 |
| EP0057045A2 (en) | 1982-08-04 |
| JPH03173880A (en) | 1991-07-29 |
| EP0023849B1 (en) | 1983-05-04 |
| US4556732A (en) | 1985-12-03 |
| EP0057491A3 (en) | 1982-08-18 |
| JPS62161778A (en) | 1987-07-17 |
| EP0023849A2 (en) | 1981-02-11 |
| JPS5629544A (en) | 1981-03-24 |
| ATE8781T1 (en) | 1984-08-15 |
| JPH0417953B2 (en) | 1992-03-26 |
| HU180358B (en) | 1983-02-28 |
| EP0023849A3 (en) | 1981-05-06 |
| EP0057491A2 (en) | 1982-08-11 |
| JPS63239279A (en) | 1988-10-05 |
| EP0057491B1 (en) | 1984-08-01 |
| FR2458533B1 (en) | 1983-07-18 |
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